Telechelic n-alkylated polyamide polymers and copolymers

ABSTRACT

Low glass transition temperature polyamide oligomers or telechelic polyamides are formed from monomers forming tertiary amide linkages. These polyamides can be used with co-reactants to form high molecular weight or crosslinked polymers with desirable polyamide properties.

FIELD OF INVENTION

The invention relates to telechelic polyamides that are liquid belowabout 70° C. and can be reacted into other polymeric materials to impartdesirable properties. Many polyamides, e.g. the various nylon polymers,are solids at temperatures of below about 80° C. and thus would bedifficult to homogenously react into other polymeric materials.N-alkylating the nitrogen atom of the polyamide or the nitrogen bearingprecursor of the polyamide eliminates the hydrogen bonding making thepolyamide of this disclosure lower melting and more soluble.

BACKGROUND OF THE INVENTION

Vol. 38 (October 1946) of Industrial and Engineering Chemistry, pp.1016-1019 titled Melting Points of N-Substituted Polyamides, by authorsB. S. Biggs, C. J. Frosch, and R. H. Erickson studies the effectsubstitution on a nitrogen of a polyamide and the correlation of thepolyamide melting points with the degree and type of substitution.

A compilation titled Research in the Field of Synthesis of Condensationof a N-alkylated Hexamethylenediamine by authors A. L. Klebanskii and M.S. Vilesova (1957), comprising: VI. Synthesis of Polyamines Startingwith N-Alkylated Hexamethylenediamine, Production of Partly N-alkylatedPolyamides pp. 1820-1823 describing fundamental properties of polyamides(crystallinity, tensile strength, stability in organic solvents et al.);and VII. Preparation of Completely N-alkylated Polyamides and Couplingof Their Chains with a Diisocyanate pp. 1824-1828 describes lengtheningof polyamide chains by coupling with diisocyanates.

U.S. Pat. No. 4,992,500 describes Aqueous Dispersions of PolyamidesEmulsified with Rosin Derivatives.

Vol. 184 of Makromol. Chem. (1983) pp 1957-1965 discloses polymerizationof a polyamide from N-methyldodecanelactam. Vol. 41 of Polymer (2000) pp7653-7866 titled Crystallization Behavior ofPoly(N-methyldodecano-12-lactam) discloses homopolymers ofN-methyldodecano-12-lactam.

Vol. 28 of J. of Polym. Sci. Part A: Polym. Chem. (1990) pp 1473-1482titled Polyurethane Elastomers with Hydrolytic and ThermoxidativeStability. I. Polyurethanes with N-Alkylated Polyamide Soft Blocksdiscloses polyurethanes with N-alkylated polyamide linkages.

Vol. 28 of J. of Polym. Sci. Part A: Polym. Chem. (1990) titledPolyurethane Elastomers with Hydrolytic and Thermoxidative Stability.II. Polyurethanes with N-Alkylated Polyamide Soft Blocks disclosescopolyamides where the alkyl group on the amine is methyl, ethyl,isopropyl, or butyl and the diacid is a carbonate.

U.S. Pat. No. 5,610,224 discloses an ionic and nonionic polyamidemodified polyurethane polymers for use in coating compositions, methodfor forming, and coating compositions containing these polymers.

EP 594 292 A1 describes N-alkylated aminoalcohols reacted with alactone. That reaction product is reacted with a diester of adicarboxylic acid or an anhydride of a dicarboxylic acid.

U.S. Pat. No. 7,276,570 titled Compositions for Golf Equipment andassigned to Acushnet Company discloses golf balls comprisingthermoplastic, thermoset, castable, or millable elastomer compositionscomprising at least one polymer having a plurality of anionic moietiesattached thereto. The compositions can be used as part of golf ballconstruction.

Vol. 22 of International J. of Adhesion & Adhesives (2002) pp 75-79titled Polyamides Derived from Piperazine and Used for Hot-meltAdhesives: Synthesis and Properties discloses copolymers of piperazinewith ethylene diamine and dimeric fatty acids.

WO2006/053777 A1 to Novartis Pharma Gmbh discloses crosslinkablepoly(oxyalkylene) containing polyamide prepolymers that can be used toprovide water-soluble prepolymers that can be used as a component incontact lenses. US 2008/0090956 A1 discloses water-dilutable,hydroxy-functional polyurethanes containing amide structural units, aprocess for preparing them, and aqueous coating compositions preparedfrom them.

US 2008/0223519 (equivalent WO2008/070762) titled Polyamide Polyols andPolyurethanes, Methods for Making and Using, and Products Made Therefromdiscloses reaction products of a polymeric and non-polymeric diaminewith dicarboxylic acid and hydroxy substituted carboxylic acid. It alsodiscloses reactions of the polyamide with diisocyanates.

EP 449419 A1 describes reacting primary aminoalcohols with acidterminated polyamideethers to create hydroxyl terminated polymers.

SUMMARY OF THE INVENTION

This invention relates to low molecular weight polyamide oligomers andtelechelic polyamides (including copolymers) comprising N-alkylatedamide groups in the backbone structure. These polymers are useful assoft segments in the preparation of thermoplastic, thermoset, orelastomer resins and water-borne dispersions of those resins. The uniquefeature of these polyamide polymers is their ability to be processed asliquids at temperatures from 20 to 50 or 80° C., which makes themsuitable for further reaction and polymerization forming variousthermoplastic or thermoplastic elastomer compositions.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The following terms have definitions as stated below: Telechelicpolymers, defined as macromolecules that contain two reactive end groupsand are used as cross-linkers, chain extenders, and important buildingblocks for various macromolecular structures, including block and graftcopolymers, star, hyperbranched or dendritic polymers, Telechelicpolymers of the polydiene, polyester, polyether, and polycarbonate typeare well known in the art. These prior art telechelic polymers withfunctional end groups selected from primary or secondary hydroxyl,primary or secondary amine, and carboxylic acid have been reacted withcomplimentary reactants to form larger polymers with the properties oftelechelic precursors. Easy to process polyamide telechelics with lowmelting points have not been available.

We will use the parentheses to designate 1) that the something isoptionally present such that monomer(s) means monomer or monomers or(meth)acrylate means methacrylate or acrylate, 2) to qualify or furtherdefine a previously mentioned term, or 3) to list narrower embodiments.

Polyester polyols render good mechanical properties and UV resistance,but they suffer from poor hydrolysis resistance. Polyether polyols havebetter hydrolytic stability than polyesters, but fall short in UVresistance. Polycarbonate polyols offer improved hydrolysis resistanceover polyesters with some degree of increased hardness, but they are anorder of magnitude more expensive than other polyols. Polydiene polyolsare useful but are too hydrophobic to interact well with polarsubstrates. Some polydiene polyols are hydrogenated to reducedegradation mechanisms relying on residual unsaturation from the dienemonomer. Therefore, a new class of telechelic polyamide will helpovercome these problems.

Amine terminated polyamide oligomers were made with low viscosity, lowglass transition temperature, suppressed crystallinity, low acid number,with various nitrogen or amide:hydrocarbon weight ratios (orhydrophilic/hydrophobic balance), and with a controlled number ofhydrogen bonding or non-hydrogen bonding amide groups.

A series of polyamide oligomers from conventional difunctional acids andamines were made. The initial oligomers contained amine terminations andin reaction with diisocyanates form polyamide-polyurea backbone.However, the presence of strong hydrogen bond in these structures makesthem very hard (high glass transition) even at low molecular-weight andtherefore not suitable for further structural modifications orpreparation higher molecular weight polymers or crosslinked networks. Wediscovered that substitution of N-alkyl groups on these polymers makethem soft and easy to process.

This invention relates to polyamide oligomers or telechelic polyamidesresistant to chain scission, e.g. by hydrolysis or UV degradation,useful as macromonomers, prepolymers or polymer segments to make highermolecular weight polymers and/or crosslinked polymer networks. Theresulting polymers or networks have better thermal stability thansimilar polymers or networks from polyethers and/or polyesters due tothe higher thermal stability of the amide bonds. Polymers built frommoderate molecular weight polyamide oligomers and co-reactants that canform chemical bonds with co-reactive groups at the termini of theoligomers. These polymers have many of the properties of the polyamideoligomers from which they are made as the oligomers form a substantialweight percent of the final polymer. Modifying the molecular weight andcomposition of the oligomers can be used to achieve the desiredproperties. They can also be used to make polyurea/urethanes. The termpolyurea/urethane will be used to refer to polymers that have urealinkages, urethane linkages or blends of such linkages. The compositionmay contain small amounts of other polymers and materials either asphysical blends or where the other polymers or materials may beco-reacted into the polyamide.

The term polyamide oligomer will refer to an oligomer with two or moreamide linkages, or sometimes the amount of amide linkages will bespecified. A subset of polyamide oligomers will be telechelicpolyamides. Telechelic polyamides will be polyamide oligomers with highpercentages, or specified percentages, of two functional groups of asingle chemical type, e.g. two terminal amine groups (meaning eitherprimary, secondary, or mixtures), two terminal carboxyl groups, twoterminal hydroxyl groups (again meaning primary, secondary, ormixtures), or two terminal isocyanate groups (meaning aliphatic,aromatic, or mixtures). Ranges for the percent difunctional that arepreferred to meet the definition of telechelic are at least 70 or 80,more desirably at least 90 or 95 mole % of the oligomers beingdifunctional as opposed to higher or lower functionality. Reactive amineterminated telechelic polyamides will be telechelic polyamide oligomerswhere the terminal groups are both amine types, either primary orsecondary and mixtures thereof, i.e. excluding tertiary amine groups.

A first portion of this invention is the substitution of polyamidesegments for polyester, polyether, or polycarbonate soft segments in apolymer made from telechelic oligomers. The replacement or substitutionof polyamide segments for polyester, polyether, or polycarbonatesegments can be partial or complete. Optimum environmental resistance,including thermal stability, would result from complete replacement ofpolyester and polyether segments, due to their potential for easierchain scission in polyethers and polyesters. In some embodiments some ofthe polyester and or polyether segments could be retained in thetelechelic polyamide or polyamide oligomer for their ability to softenthe elastomeric portion or modify the compatibility of the resultingpolymer with other polymer surfaces. When polymer from polyesters orpolyether are degraded by hydrolysis or UV activated chain scission themolecular weight of the polymer is decreased such that the polymer, orsegment, soon loses its tensile strength, elongation to break,resistance to solvents, etc.

A second benefit of the first portion of this invention, substitutingsoft polyamide segments for soft polyether or polyester segments, isthat the polyamide segments tend to promote better wetting and adhesionto a variety of polar substrates, such as glass, nylon, and metals thanpolyester or polyether based polymers. The hydrophobic/hydrophilicnature of the polyamide can be adjusted by using different weight ratiosof hydrocarbon to amide linkages, or nitrogen atoms, in the polyamide.Diacids, diamines, aminocarboxylic acids, and lactams with largealiphatic hydrocarbons portions relative to the amide linkage portiontend to be hydrophobic. When the hydrocarbon weight ratio to amidelinkage, or nitrogen atoms, becomes smaller, the polyamide is morehydrophilic. Increasing the amount of polyamide in a polymer canincrease adhesion to substrates that have similar or compatible surfacesto polyamides.

Polymers made from polyamide segments can have good solvent resistance.Solvents can cause deformation and swelling of a polymer thereby causingpremature failure of the polymer. Solvents can cause a coating to swelland delaminate from a substrate at the interface between the two.

It should be noted that many of the polyamides of the prior art are highmelting point crystalline polyamides such as 6-nylon, 6,6-nylon,6,10-nylon that melt at temperatures much too high, e.g. in excess of100° C., to serve as soft segments if a blocky thermoplastic polymer isdesired. In some of the prior art publications the polyamide, often acrystalline or high Tg polyamide type, was added merely to increase thesurface interaction with a substrate that was compatible to polyamides.To create a lower Tg polymer, soft (low Tg) polyester, polyether orpolycarbonates were added to the polyamide segment to provide a lowercomposite Tg elastomeric segment. In other prior art publications only afew polyamide linkages were inserted into a polymer to modify thepolarity of the polymer, to increase solvent resistance, or to raise thesoftening temperature.

One objective of the current patent application is to use highpercentages of amide linkages in a telechelic oligomer comprised of oneor more polyamide segments to provide resistance to chain scission fromhydrolysis and/or UV activated chain scission. Thus, many embodimentswill describe soft segments with high percentages of total linkagesbetween repeat units in the soft segment being amide linkages. Someembodiments may allow for some linkages between repeat units to be otherthan amide linkages.

An important modification from conventional polyamides to get low Tgpolyamide soft segments is the use of monomers with secondary amineterminal groups in forming the polyamide. The amide linkage formed froma secondary amine and a carboxylic acid type group is called a tertiaryamide linkage. Primary amines react with carboxylic acid type groups toform secondary amides. The nitrogen atom of a secondary amide has anattached hydrogen atom that often hydrogen bonds with a carbonyl groupof a nearby amide. The intra-molecular H-bonds induce crystallinity withhigh melting point and can act as crosslinks reducing chain mobility.With tertiary amide groups the hydrogen on the nitrogen of the amidelinkage is eliminated along with hydrogen bonding. A tertiary amidelinkage that has one additional alkyl group attached to it as comparedto a secondary amide group, which has hydrogen attached to it, hasreduced polar interactions with nearby amide groups when the polymerexists in a bulk polymer sample. Reduced polar interactions mean thatglassy or crystalline phases that include the amide linkage melt atlower temperatures than similar amide groups that are secondary amidegroups. One way to source secondary amine reactant, a precursor totertiary amide linkages, is to substitute the nitrogen atom(s) of theamine containing monomer with an alkyl group. Another way to source asecondary amine reactant is to use a heterocyclic molecule where thenitrogen of the amine is part of the ring structure. Piperazine is acommon cyclic diamine where both nitrogen atoms are of the secondarytype and part of the heterocyclic ring.

Another modification to reduce the Tg of the polyamide soft segments isto use at least one additional monomer beyond the minimum number ofmonomers to form the polyamide. Thus, for a polyamide formed from alactam polymerization, such as from N-methyl-dodecyl lactam one wouldinclude an additional lactam, aminocarboxylic acid, diamine, ordicarboxylic acid in the monomers for the polymerization to change thespacing (among repeat units) between the amide linkages formed by themonomer so that the spacing between the amide linkages in the polyamideis irregular along the backbone, e.g. not the same physical dimensionfor some of the repeat units in each oligomer. For a polymerization ofaminocarboxylic acid one would include additional lactam,aminocarboxylic acid, diamine, or dicarboxylic acid (with differentphysical length between the primary reactive groups of the monomer) inthe monomer blend for the polymerization to change the spacing amongrepeat units between the amide linkages. Switching end groups on themonomers can also disrupt regularity in the spacing of the polar amidelinkages and lower the effective Tg of the copolymer. Thus,co-polymerizing a C₆ amino carboxylic acid with a small portion of a C₆diacid and C₆ diamine can disrupt regularity of the amide linkages asthe diacid and diamine units would switch the orientation of the amidelinkage from head to tail orientation to tail to head orientation,slightly disrupting uniformity of spacing of the amide linkages alongthe polyamide backbone. Typically, when following this procedure, onewould try to add a disrupting monomer that increased or decreased thenumber of atoms between the amide forming end groups of the monomer(s)used as the primary monomer in the polyamide. One could also use asecond disrupting monomer that had a cyclic structure, such aspiperazine, a cyclic diamine monomer with where two methylene atoms formthe top half of the ring and two methylene atoms form the bottom half ofthe ring, to disrupt the regularity of polyamide formed from a diacidreacted with a diamine monomer with two methylene atoms between thenitrogen atoms of the diamine.

Another way to express the use of a copolymerization method to reducethe Tg and consequently the hardness of the polyamide is that thepolyamide is characterized as being within a, b or c:

a) when said amide linkages are derived from polymerizing one or moremonomers and more than 90 mole % of said monomers are derived frompolymerizing monomers selected from lactam and aminocarboxylic acidmonomer then said polyamide is defined as a copolymer of at least twodifferent monomers (meaning said monomers are characterized as being atleast two different monomers because they have hydrocarbyl portion ofdifferent spacing length between the amine and carboxylic acid groups,wherein each of said at least two different monomers is present at molarconcentrations of at least 10%, more desirably at least 20 or 30% of thetotal lactam and/or aminocarboxylic acid monomers in said polyamide) orb) when said amide linkages are derived from polymerizing two or moremonomers and more than 90 mole % of said monomers were derived frompolymerizing dicarboxylic acid and diamine monomers then said polyamideis defined as a terpolymer of at least three different monomers (meaningsaid amide linkages are formed from at least three different monomersselected from the group of dicarboxylic acid and diamine monomerswherein said at least three different monomers are characterized asdifferent from each other by a hydrocarbyl group of different spacinglength between the carboxylic acid groups of the dicarboxylic acid, ordifferent spacing length between the amine groups of the diamine,wherein each of said at least three different monomers is present atconcentrations of at least 10 mole %, more desirably at least 20 or 30mole %, of the total monomers in said polyamide), orc) with the proviso that if said amide linkages are derived frompolymerizing a combination of dicarboxylic acid, diamine and eitherlactam and/or aminocarboxylic acid monomers such that the totaldicarboxylic acid monomer(s) and the diamine monomer(s) are present inthe monomer blend at concentrations of at least 10 mole %, moredesirably at least 20 or 30 mole %, and the total lactam andaminocarboxylic acid monomers are present in the monomer blend atconcentrations of at least 10 mole %, more desirably at least 20 or 30mole %, then there are no restrictions requiring additional differentmonomers.

Generally, having nearly equal amounts of two or more different amideforming monomers results in different spacing between the amide linkagesalong the polyamide backbone and affords optimal reduction of thecrystalline melting and glass transition temperatures. For example, a50:50 mole blend of two different diamines would be desirable. A 50:50mole blend of two different diacids would be desirable. A 33:33:33 moleblend of a lactam with a diacid and a diamine would be desirable.

We use the term low Tg, glass transition temperature, even though werealize most of the polyamide segments are initially low molecularweight and it would not be easily possible to measure the Tg of the lowmolecular weight oligomers, the measured value would be dramaticallyaffected by molecular weight. High Tg polymers, e.g. having Tg valuesabove 70, 80, or 90° C. as measured by differential scanning calorimetry(DSC), would tend to form solids or gels even at low molecular weights.Thus, the polyamide oligomers, telechelic polyamides, and even theoligomers from telechelic polyamides or polyamide oligomers are oftendescribed in this specification by their viscosity at specifictemperatures. Low Tg polyamides oligomers will be defined as thosecompositions that would have Tg, if above 20,000 g/mole molecularweight, of below 50° C., more desirably below 25 or 0° C.

In one embodiment the telechelic oligomer or telechelic polyamide willhave a viscosity measured by a Brookfield circular disc viscometer withthe circular disc spinning at 5 rpm of less than 100,000 cps at atemperature of 70° C., more desirably less than 15,000 or 10,000 cps at70° C., still more desirably less than 100,000 cps at 60 or 50° C., andmore preferably less than 15,000 or 10,000 cps at 60° C.; and still morepreferable less that 15,000 or 10,000 cps at 50° C. Desirably, theseviscosities are those of neat telechelic prepolymers or polyamideoligomers without solvent or plasticizers. These viscosity values willfacilitate mixing the telechelic polyamide with co-reactants and orparticulate materials under suitable conditions that desirable reactionsoccur at reasonable rates and undesirable reactions, e.g. sidereactions, do not occur to any significant extent. In some embodimentsthe telechelic polyamide can be diluted with solvent to achieveviscosities in these ranges.

Many of the oligomers, telechelics, and polymers of this specificationare made by condensation reactions of reactive groups on desiredmonomer(s). Lactam polymerization into a polyamide results in similaramide linkages by a chain polymerization process and is well known inthe art. These condensation reactions between carboxylic acid groups andamine or hydroxyl groups are well known and are driven by the removal ofwater and or catalysts. The formation of amides from the reaction ofcarboxylic acid groups and amine groups can be catalyzed by boric acid,boric acid esters, boranes, phosphorous acid, phosphates, phosphateesters, amines, acids, bases, silicates, and silsesquioxanes. Additionalcatalysts, conditions, etc. are available in textbooks such as“Comprehensive Organic Transformations” by Larock.

The condensation reaction of reactive groups will be defined as creatingchemical linkages between the monomers. The portion of the monomer thatis incorporated into the oligomer or polymer will be defined as therepeat unit from the particular monomer. Some monomers, such asaminocarboxylic acid, or one end of diacid reacting with one end of adiamine, lose one molecule of water as the monomer goes from a monomerto a repeat unit of a polymer. Other monomers, such as lactams,isocyanates, amines reacted with isocyanates, hydroxyl groups reactedwith isocyanates, etc. do not release a portion of the molecule to theenvironment but rather retain all of the monomer in the resultingpolymer.

We will define polyamide oligomer as a species below 20,000 g/molemolecular weight, e.g. often below 10,000; 5,000; 2,500; or 2000 g/mole,that has two or more amide linkages per oligomer. Later we will definepreferred percentages of amide linkages or monomers that provide onaverage one amide linkage per repeat unit in various oligomeric species.A subset of polyamide oligomer will be telechelic oligomer. Thetelechelic polyamide has molecular weight preferences identical to thepolyamide oligomer above. The term telechelic has been earlier defined.Multiple polyamide oligomers or telechelic polyamides can be linked withcondensation reactions to form polymers, generally above 100,000 g/mole.

Generally, amide linkages are formed from the reaction of a carboxylicacid group with an amine group or the ring opening polymerization of alactam, e.g. where an amide linkage in a ring structure is converted toan amide linkage in a polymer. In a preferred embodiment a large portionof the amine groups of the monomers are secondary amine groups or thenitrogen of the lactam is a tertiary amide group. Secondary amine groupsform tertiary amide groups when the amine group reacts with carboxylicacid to form an amide. For the purposes of this disclosure, the carbonylgroup of an amide, e.g. as in a lactam, will be considered as derivedfrom a carboxylic acid group. The amide linkage of a lactam is formedfrom the reaction of carboxylic group of an aminocarboxylic acid withthe amine group of the same aminocarboxylic acid. In one embodiment wewant less than 20, 10 or 5 mole percent of the monomers used in makingthe polyamide to have functionality in polymerization of amide linkagesof 3 or more. This will reduce branching in the polyamide oligomer ortelechelic polyamide.

The polyamide oligomers and telechelic polyamides of this disclosure cancontain small amounts of ester linkages, ether linkages, urethanelinkages, urea linkages, etc. if the additional monomers used to formthese linkages are useful to the intended use of the polymers. Thisallows other monomers and oligomers to be included in the polyamide toprovide specific properties, which might be necessary and not achievablewith a 100% polyamide segment oligomer. Sometimes added polyether,polyester, or polycarbonate provides softer e.g. lower Tg, segments.Sometimes it is desirable to convert the carboxylic end groups orprimary or secondary amine end groups of a polyamide to other functionalend groups capable of condensation polymerizations. A telechelicpolyamide with carboxylic end groups can be converted into an oligomerwith hydroxyl end groups by reacting the telechelic polyamide with apolyether that has two hydroxyl end groups or a polyether that has oneamino, primary or secondary, and one hydroxyl end group. This is shownin Table 1, examples E, F, and G and is a preferred embodiment.Oligomers or polymers with polyether segments have susceptibility tochain breakage due to UV exposure. The effect of UV exposure on blockcopolymers of nylon 6-polyethylene glycol block copolymers is reportedin Gauvin, Pascal; Lemaire, Jacques in Makromolekulare Chemie (1987),188(5), 971-986. Sometimes an initiator for oligomer chainpolymerization of a lactam is used that doesn't generate an amidelinkage. Sometimes a polyether might be used as a segment or portion ofa polyamide to reduce the Tg, or provide a soft segment, of theresulting polyamide oligomer. Sometimes a polyamide segment, e.g.possibly difunctional with carboxylic acid or amine terminal groups, canbe functionalized with two polyether end segments (such as fromJeffamine™ D230) to further lower the Tg of, or provide a soft segmentin, the polyamide oligomer and create a telechelic polyamide with amineor hydroxyl end groups. Sometimes a carboxylic acid terminatedtelechelic polyamide segment is functionalized by reacting with an aminoalcohol, such as N-methylaminoethanol or HN(R^(α))(R^(β)) where R^(α) isa C₁ to C₄ alkyl group and R_(β) comprises an alcohol group and a C₂ toC₁₂ alkylene group, alternatively R^(α) and R^(β) can be interconnectedto form a C₃ to C₁₆ alkylene group including a cyclic structure andpendant hydroxyl group (such as in 2-hydroxymethyl piperidine), eitherof which can create a telechelic polyamide with terminal hydroxylgroups. The reaction of the secondary amine (as opposed to the hydroxylgroup) with the carboxylic acid can be favored by using a 100% molarexcess of the amino alcohol and conducting the reaction at 160° C.+/−10or 20°. The excess amino alcohol can be removed by distillation afterreaction. In one embodiment the functional primary or secondary aminegroups of a telechelic polyamide are reacted with a lactone of 2 or 4 to10 carbon atoms (e.g. a valero or caprolactone) and/or hydroxylcarboxylic acid of 3 to 30 carbon atoms to create one or two hydroxylfunctional end groups derived from said lactone or said hydroxylcarboxylic acid on said telechelic polyamide. Optimally only one repeatunit from said lactone or hydroxyl carboxylic acid is added to each endof said telechelic polyamide.

As earlier indicated many amide forming monomers create on average oneamide linkage per repeat unit. These include diacids and diamines whenreacted with each other, aminocarboxylic acids, and lactams. When wediscuss these monomers or repeat units from these monomers we generallymean these monomers, their repeat units and their reactive equivalents(meaning monomers that generate the same repeat unit as the namedmonomer). These reactive equivalents might include anhydride of diacids,esters of diacids, etc. These monomers, when reacted with other monomersin the same group, also create amide linkages at both ends of the repeatunits formed. Thus we will use both percentages of amide linkages andmole percent and weight percentages of repeat units from amide formingmonomers. Amide forming monomers will be used to refer to monomers thatform on average one amide linkage per repeat unit in normal amideforming condensation linking reactions.

In one embodiment desirably at least 10 mole %, more desirable at least25, 45 or 50, more desirably at least 55, 60, 70, 75, 80, 90, or 95 mole% of the total number of the heteroatom containing linkages connectinghydrocarbon type linkages are characterized as being amide linkages.Heteroatom linkages are linkages such as amide, ester, urethane, urea,ether linkages where a heteroatom connects two portions of an oligomeror polymer that are generally characterized as hydrocarbons (or havingcarbon to carbon bond, such as hydrocarbon linkages). As the amount ofamide linkages in the polyamide increase the amount of repeat units fromamide forming monomers in the polyamide increases.

In one embodiment desirably at least 25 wt. %, more desirable at least30, 40, 50, more desirably at least 60, 70, 80, 90, or 95 wt. % of thepolyamide oligomer or telechelic polyamide is repeat units from amideforming monomers, also identified as monomers that form amide linkagesat both ends of the repeat unit. Such monomers include lactams,aminocarboxylic acids, dicarboxylic acid and diamines.

In one embodiment desirably at least 25, 50, 65, 75, 76, 80, 90, or 95mole percent of the amide linkages in the polyamide oligomer ortelechelic polyamine are tertiary amide linkages. As earlier explainedtertiary amide linkages result from ring opening polymerization oflactams with tertiary amides or reactions of secondary amines withcarboxylic acid groups.

Calculation of Tertiary Amide Linkage %:

The % of tertiary amide linkages of the total number of amide linkageswas calculated with the following equation:

${{Tertiary}\mspace{14mu} {amide}\mspace{14mu} {linkage}\mspace{14mu} \%} = {\frac{\sum_{i = 1}^{n}\left( {w_{{tertN},i} \times n_{i}} \right)}{\left. {\sum_{i = 1}^{n}\left( {w_{{totalN},i} \times n_{i}} \right)} \right)} \times 100}$

where n is the number of monomers,the index i refers to a certain monomer,w_(tertN) is the average number nitrogen atoms in a monomer that form orare part of tertiary amide linkages in the polymerizations, (note:end-group forming amines do not form amide groups during thepolymerizations and their amounts are excluded from w_(tertN)),w_(totalN) is the average number nitrogen atoms in a monomer that formor are part of tertiary amide linkages in the polymerizations (note: theend-group forming amines do not form amide groups during thepolymerizations and their amounts are excluded from w_(totalN)), andn_(i) is the number of moles of the monomer with the index i.

Calculation of Amide Linkage %:

The % of amide linkages of the total number of all heteroatom containinglinkages (connecting hydrocarbon linkages) was calculated by thefollowing equation:

${{Amide}\mspace{14mu} {linkage}\mspace{14mu} \%} = {\frac{\sum_{i = 1}^{n}\left( {w_{{totalN},i} \times n_{i}} \right)}{\sum_{i = 1}^{n}\left( {w_{{totalS},i} \times n_{i}} \right)} \times 100}$

where w_(totalS) is the sum of the average number of heteroatomcontaining linkages (connecting hydrocarbon linkages) in a monomer andthe number of heteroatom containing linkages (connecting hydrocarbonlinkages) forming from that monomer by the reaction with a carboxylicacid bearing monomer during the polyamide polymerizations. “Hydrocarbonlinkages” are just the hydrocarbon portion of each repeat unit formedfrom continuous carbon to carbon bonds (i.e. without heteroatoms such asnitrogen or oxygen) in a repeat unit. This hydrocarbon portion would bethe ethylene or propylene portion of ethylene oxide or propylene oxide;the undecyl group of dodecyllactam, the ethylene group ofethylenediamine, and the (CH₂)₄ (or butylene) group of adipic acid.

Preferred amide or tertiary amide forming monomers include dicarboxylicacids, diamines, aminocarboxylic acids and lactams. Preferreddicarboxylic acids are where the alkylene portion of the dicarboxylicacid is a cyclic, linear, or branched (optionally including aromaticgroups) alkylene of 2 to 36 carbon atoms, optionally including up to 1heteroatom per 3 or 10 carbon atoms of the diacid, more preferably from4 to 36 carbon atoms (the diacid would include 2 more carbon atoms thanthe alkylene portion). These include dimer fatty acids, hydrogenateddimer acid, sebacic acid, etc. Generally we prefer diacids with largeralkylene groups as this generally provides polyamide repeat units withlower Tg value.

Preferred diamines include those with up to 60 carbon atoms, optionallyincluding 1 heteroatom (besides the two nitrogen atoms) for each 3 or 10carbon atoms of the diamine and optionally including a variety ofcyclic, aromatic or heterocyclic groups providing that one or both ofthe amine groups are secondary amines, a preferred formula is

wherein R_(b) is a direct bond or a linear or branched (optionally beingor including cyclic, heterocyclic, or aromatic portion(s)) alkylenegroup (optionally containing up to 1 or 3 heteroatoms per 10 carbonatoms of the diamine) of 2 to 36 carbon atoms and more preferably 2 or 4to 12 carbon atoms and R_(c) and R_(d) are individually a linear orbranched alkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4carbon atoms or R_(c) and R_(d) connect together to form a single linearor branched alkylene group of 1 to 8 carbon atoms or optionally with oneof R_(c) and R_(d) is connected to R_(b) at a carbon atom, moredesirably R_(c) and R_(d) being 1 or 2 to 4 carbon atoms.

Such diamines include Ethacure™ 90 from Albermarle (supposedly aN,N′-bis(1,2,2-trimethylpropyl)-1,6-hexanediamine); Clearlink™ 1000 fromDorfketal, or Jefflink™ 754 from Huntsman; N-methylaminoethanol;dihydroxy terminated, hydroxyl and amine terminated or diamineterminated poly(alkyleneoxide) where the alkylene has from 2 to 4 carbonatoms and having molecular weights from about 40 or 100 to 2000;N,N′-diisopropyl-1,6-hexanediamine; N,N′-di(sec-butyl) phenylenediamine;piperazine; homopiperazine; and methyl-piperazine. Jefflink™754 has thestructure

Clearlink™ 1000 has the structure

Another diamine with an aromatic group is: N,N′-di(sec-butyl)phenylenediamine, see structure below:

Preferred diamines are diamines wherein both amine groups are secondaryamines.

Preferred lactams include straight chain or branched alkylene segmentstherein of 4 to 12 carbon atoms such that the ring structure withoutsubstituents on the nitrogen of the lactam has 5 to 13 carbon atomstotal (when one includes the carbonyl) and the substituent on thenitrogen of the lactam (if the lactam is a tertiary amide) is an alkylof from 1 to 8 carbon atoms and more desirably an alkyl of 1 to 4 carbonatoms. Dodecyl lactam, alkyl substituted dodecyl lactam, caprolactam,alkyl substituted caprolactam, and other lactams with larger alkylenegroups are preferred lactams as they provide repeat units with lower Tgvalues. Aminocarboxylic acids have the same number of carbon atoms asthe lactams. Desirably the number of carbon atoms in the linear orbranched alkylene group between the amine and carboxylic acid group ofthe aminocarboxylic acid is from 4 to 12 and the substituent on thenitrogen of the amine group (if it is a secondary amine group) is analkyl group with from 1 to 8 carbon atoms, more preferably 1 or 2 to 4carbon atoms. Aminocarboxylic acids with secondary amine groups arepreferred.

In one embodiment desirably at least 50 wt. %, more desirably at least60, 70, 80 or 90 wt. % of said polyamide oligomer or telechelicpolyamide comprise repeat units from diacids and diamines of thestructure of the repeat unit being

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched (optionally including aromatic groups)alkylene of 2 to 36 carbon atoms, optionally including up to 1heteroatom per 3 or 10 carbon atoms of the diacid, more preferably from4 to 36 carbon atoms (the diacid would include 2 more carbon atoms thanthe alkylene portion) and

wherein R_(b) is a direct bond or a linear or branched (optionally beingor including cyclic, heterocyclic, or aromatic portion(s)) alkylenegroup (optionally containing up to 1 or 3 heteroatoms per 10 carbonatoms) of 2 to 36 or 60 carbon atoms and more preferably 2 or 4 to 12carbon atoms and R_(c) and R_(d) are individually a linear or branchedalkyl group of 1 to 8 carbon atoms, more preferably 1 or 2 to 4 carbonatoms or R_(c) and R_(d) connect together to form a single linear orbranched alkylene group of 1 to 8 carbon atoms or optionally with one ofR_(c) and R_(d) is connected to R_(b) at a carbon atom, more desirablyR_(c) and R_(d) being an alkyl group of 1 or 2 to 4 carbon atoms.

In one embodiment desirably at least 50 wt. %, more desirably at least60, 70, 80 or 90 wt. % of said polyamide oligomer or telechelicpolyamide comprise repeat units from lactams or amino carboxylic acidsof the structure

Repeat units can be in a variety of orientations in the oligomer derivedfrom lactams or amino carboxylic acid depending on initiator type,wherein each R_(e) independently is linear or branched alkylene of 4 to12 carbon atoms and each R_(f) independently is a linear or branchedalkyl of 1 to 8, more desirably 1 or 2 to 4, carbon atoms.

The above described polyamide oligomers and telechelic polyamide areuseful to make polymers by reacting the polyamide oligomer or telechelicpolyamide with co-reactants having two or more reactive groups that canform chemical bonds when reacted with the functional groups of thepolyamide oligomers or telechelic polyamide (e.g. these functionalgroups of the polyamide include primary and secondary amine, primary orsecondary hydroxyl, or carboxylic acid group). The reactive groups onthe co-reactants may be isocyanate, or with particular telechelicpolyamides they could be hydroxyl, amine or carboxylic acid groups.

We made a series of polyamide oligomers from conventional difunctionalacids and amines. These oligomers contained amine terminations and inreaction with diisocyanates form polyamide-polyurea backbone. Thepolyamide building blocks in our new dispersion polymers provideexcellent hydrolytic stability, superior heat and UV resistance, andbetter overall mechanical properties in comparison to polyester andpolyether segments. In addition, the amine chain termination in thesepolyamide oligomers, when reacted with isocyanates, forms urea linkages,vs. urethane link from polyol reacted with isocyanates. These polyurealinkages are known to have stronger intermolecular attractions that actmore like a true crosslinked polymer, resulting in performanceadvantages over urethanes, including but not limited to better solventresistance and elasticity.

Conventional Blends with Other Polymers

The polyamide oligomer or telechelic polyamide of this invention can becombined with compatible polymers and polymer dispersions by methodswell known to those skilled in the art. Such polymers, polymersolutions, and dispersions include those described in A. S. Teot.“Resins, Water-Soluble” in: Kirk-Othmer Encyclopedia of ChemicalTechnology. John Wiley & Sons. 3rd Ed., Vol. 20, H. F. Mark et al. Eds.,pp. 207-230 (1982).

Applications

The oligomeric polyamides or telechelic polyamides of the presentinvention are useful as components in polymer compositions used ascoatings, films, fibers, adhesives, or molded or extruded goods.

Working Examples

In these examples, the following reagents were used:

Jeffamine-D230: di-primary amine-terminated polypropyleneglycol, Mn=230g/mol.IPA: Isopropyl alcoholDBTL: Dibutyltin dilaurateEC-90: Ethacure™ 90 from AlbermarleN,N′-bis(1,2,2-trimethylpropyl)-1,6-hexanediamine)PTMO-270: Poly(tetramethylene oxide) diol of about 270 g/mole molecularweight

Polyamide A

All diacids, piperazine (quantity: sum of “blocks” and “diamines” in therecipe) and the water were charged to the reactor under N₂ atmosphere.The reactor was heated to 100° C. and the water was evaporated. Heatingwas continued to 170° C. and was maintained at this temperature for 3 h.The pressure of the reactor was decreased to 1-30 mbar and the reactionwas continued for an additional 10 h. The product was a slightlyyellowish paste at room temperature with an acid number <3.0 mg KOH/gpolymer. The end-groups were secondary amines.

Polyamide B

All diacids, EC-90 and the boric acid were charged to the reactor underN₂ atmosphere. The reactor was heated to 250° C. and was maintained atthat temperature for 5 h. The reactor was cooled to 130° C. and thepiperazine was charged to the reactor (quantity: sum of “blocks” and“diamines” in the recipe). The reactor was heated to 170° C. and thepolymer was reacted for 2 h at atmospheric pressure. The pressure of thereactor was decreased to 1-30 mbar and the reaction was continued for anadditional 10 h. The product was a slightly yellowish paste at roomtemperature with an acid number <3.0 mg KOH/g polymer. The end-groupswere secondary amines.

Polyamide C

All diacids, piperazine, homopiperazine, 2-methylpiperazine and thewater were charged to the reactor under N₂ atmosphere. The reactor washeated to 100° C. and the water was evaporated. Heating was continued to180° C. and the reactor was maintained at this temperature for 3 h. Thereactor was cooled to 130° C. and the ethylenediamine was charged to thereactor. The reactor was heated to 170° C. and the polymer was reactedfor 2 h at atmospheric pressure. The pressure of the reactor wasdecreased to 1-30 mbar and the reaction was continued for an additional10 h. The product was a slightly yellowish paste at room temperaturewith an acid number <3.0 mg KOH/g polymer. The end-groups were primaryamines.

Polyamide D

All diacids, piperazine and the water were charged to the reactor underN₂ atmosphere. The reactor was heated to 100° C. and the water wasevaporated. Heating was continued to 180° C. and this temperature wasmaintained for 3 h. The reactor was cooled to 130° C. and theJeffamine-D230 was charged to the reactor. The reactor was heated to170° C. and the polymer was reacted for 2 h at atmospheric pressure. Thepressure of the reactor was decreased to 1-30 mbar and the reaction wascontinued for an additional 10 h. The product was a slightly yellowishpaste at room temperature with an acid number <3.0 mg KOH/g polymer. Theend-groups were primary amines.

TABLE 1 Polyamide oligomers Polyamide Polyamide A Polyamide B PolyamideC Polyamide D Mn g/mole 920 1700 1780 1650 Monomer 1 Sebacic acidSebacic acid Sebacic acid Sebacic acid 94.8 g 271.5 g 202.6 g 142.6 gMonomer 2 Dodecanedioic Dodecanedioic Dodecanedioic — acid 162.4 g acid109.5 g acid 74.2 g Monomer 3 Hydrogenated Hydrogenated HydrogenatedHydrogenated dimer acid dimer acid 694.9 g dimer acid dimer acid 387.3 g647.3 g 584.9 g Monomer 4 Piperazine Piperazine 270.0 g Piperazine 72.9g Piperazine 72.9 g 278.1 g Monomer 5 — EC-90 Mw 274 Homo- Jeffamine D230 103.6 g piperazine Mn 230 302.6 g 26.3 g Monomer 6 — — Methyl- —piperazine 55.6 g Monomer 7 — — Ethylene- — diamine 60.1 g Catalyst —Boric acid 1.3 g — — Water 350 g 0 g 350 g 400 g Terminal DiamineDiamine Diamine Diamine primary secondary secondary primary Tg −17.3° C.−14.0° C. −13° C. −20° C. Viscosity 26,000 cps 55,000 cps@70° C. —21,000@55° C. @60° C. Tertiary amide 100% 100%  77% 56% linkages % Amide100% 100% 100% 43% linkages % Polyamide Polyamide E Polyamide FPolyamide G1 Polyamide G2 Mn g/mole 1500 g/mole 1700 g/mole 450 g/mole1500 g/mole Monomer 1 Dodecanedioic Sebacic acid Sebacic acid PolyamideG1 acid 46.0 g 37.2 g 246.6 g Monomer 2 Ethyllauryllactam DodecanedioicDodecanedioic 161.1 acid 20.7 g acid 240.6 g Monomer 3 LauryllactamDimer acid Piperazine 92.0 g 8.5 g 183.3 g Monomer 4 JeffaminePiperazine 19.8 g PTMO-270 503.7 g D230 92.0 g Monomer 5 — Homo- —piperazine 5.4 g Monomer 6 Methyl- — piperazine 10.7 Monomer 7 —Jeffamine D230 — 94.7 g Catalyst — — 0.15 g DBTL Water 105 g 122.5 g 300g — Terminal Primary amine Primary amine Carboxylic acid Primaryhydroxyl (two) Tg −44° C. −34° C. −41° C. Viscosity 5,000 cps@55° C.8,800 cps@55° C. — 4,000 cps@55° C. Tertiary amide 70% 65% 100% 100%linkages % Amide 49% 49% 100%  23% linkages %General procedure for Polyamide E. The backbone of the polymer was madeby ring opening polymerization of lactams where the nitrogen in theamide group was partially or entirely alkylated. Endblocks were addedand the mixture was kept at 170° C. for 3 h at atmospheric pressure.Vacuum was applied and the temperature was maintained for 3 h. Thepolymer was cooled to room temperature.General procedure for Polyamide F: Diacids, diamines and water washeated to 200° C. for 2 h. Endblocks were added and the mixture was keptat 170° C. for 3 h at atmospheric pressure. Vacuum was applied and thetemperature is maintained for 3 h. Polymer is cooled to RT.

Polyamide G1

All diacids, piperazine and the water were charged to the reactor underN₂ atmosphere. The reactor was heated to 100° C. and the water wasevaporated. Heating was continued to 180° C. and this temperature wasmaintained for 3 h. The product is a white paste at room temperaturewith carboxylic acid end groups.

Polyamide G2

Polyamide G1 and PTMO was charged to the reactor. The reactor was heatedto 180° C. and the polymer was reacted for 3 h at atmospheric pressure.The DBTL catalyst was added and the pressure of the reactor wasdecreased to 1-30 mbar. The reaction was continued for an additional 4 hat 180° C. and then for 4 h at 200° C. The product was a slightlyyellowish paste at room temperature with an acid number <3.0 mg KOH/gpolymer. The end-groups were primary alcohols.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise indicated, allnumerical quantities in this description specifying amounts, reactionconditions, molecular weights, number of carbon atoms, etc., are to beunderstood as modified by the word “about.” Unless otherwise indicated,all percent and formulation values are on a molar basis. Unlessotherwise indicated, all molecular weights are number average molecularweights. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent, which may be customarilypresent in the commercial material, unless otherwise indicated. It is tobe understood that the upper and lower amount, range, and ratio limitsset forth herein may be independently combined. Similarly, the rangesand amounts for each element of the invention can be used together withranges or amounts for any of the other elements. As used herein, theexpression “consisting essentially of” permits the inclusion ofsubstances that do not materially affect the basic and novelcharacteristics of the composition under consideration. All of theembodiments of the invention described herein are contemplated from andmay be read from both an open-ended and inclusive view (i.e. using“comprising of” language) and a closed and exclusive view (i.e. using“consisting of” language). As used herein parentheses are useddesignate 1) that the something is optionally present such thatmonomer(s) means monomer or monomers or (meth)acrylate meansmethacrylate or acrylate, 2) to qualify or further define a previouslymentioned term, or 3) to list narrower embodiments.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention.

What is claimed is:
 1. A telechelic polyamide comprising: a) repeatunits derived from polymerizing monomers connected by linkages betweenthe repeat units and functional end groups selected from carboxyl orprimary or secondary amine, wherein at least 70 mole percent oftelechelic polyamide have exactly two functional end groups of the samefunctional type selected from the group consisting of primary orsecondary hydroxyl end groups; b) a polyamide segment comprising atleast two amide linkages characterized as being derived from reacting anamine with a carboxyl group, and said polyamide segment comprisingrepeat units derived from polymerizing two or more of monomers selectedfrom lactams, aminocarboxylic acids, dicarboxylic acids, and diamines;c) wherein at least 10% of the total number of the heteroatom containinglinkages connecting hydrocarbon type linkages are characterized as beingamide, and d) wherein at least 60 wt. % of said telechelic polyamidesegment comprises repeat units of the structure

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched alkylene of 2 to 36 carbon atoms, optionallyincluding up to 1 heteroatom per 3 or 10 carbon atoms of the diacid, ande) wherein R_(b) is a linear or branched alkylene of 2 to 60 carbonatoms and optionally being or including cyclic, heterocyclic, alkylenegroup and optionally containing up to 1 or 3 heteroatoms per 10 carbonatoms; and R_(c) and R_(d) connect together to form a single linear orbranched alkylene group of 1 to 8 carbon atoms.
 2. A telechelicpolyamide according, to claim 1, wherein at least 76% of said amidelinkages are characterized as tertiary amide linkages and said polyamideportion is characterized as being within a) or b); a) when said amidelinkages are derived from polymerizing amide forming monomers and atleast 90 mole % of said amide forming monomers were combined amounts ofdicarboxylic acid and diamine monomers then said polyamide is defined asa terpolymer of at least three different monomers, or b) when said amidelinkages are derived from polymerizing a combination of dicarboxylicacid, diamine and either lactam and/or aminocarboxylic acid monomerssuch that the total dicarboxylic acid monomer(s) and the diaminemonomer(s) are present at 10 mole % or more and the total lactam andaminocarboxylic acid monomers are present in the monomer blend at 10mole % or more, then there are no restrictions requiring additionaldifferent monomers.
 3. A telechelic polyamide, according to claim 1,wherein the total repeat units derived from monomers selected from thegroup of said lactam, aminocarboxylic acid, dicarboxylic acid, anddiamine in said amide linkages in said telechelic polyamide comprises atleast 80 wt. % of said telechelic polyamide.
 4. A telechelic polyamideaccording to claim 1, wherein at least 70 wt. % of said telechelicpolyamide segment comprises repeat units of the structure

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched alkylene of 2 to 36 carbon atoms, optionallyincluding up to 1 heteroatom per 3 or 10 carbon atoms of the diacid,more preferably from 4 to 36 carbon atoms and wherein R_(b) is a linearor branched optionally being or including cyclic, heterocyclic, alkylenegroup of 2 to 60 carbon atoms and optionally containing up to 1 or 3heteroatoms per 10 carbon atoms and R_(c) and R_(d) connect together toform a single linear or branched alkylene group of 1 to 8 carbon atoms.5. A telechelic polyamide, according to any of claim 1, wherein said twofunctional end groups of said polyamide were primary or secondary aminegroups and said telechelic polyamide was reacted with a lactone of 2 to10 carbon atoms and/or hydroxyl carboxylic acid of 3 to 30 carbon atomsto create one or more hydroxyl functional end group derived from saidlactone or said hydroxyl carboxylic acid.
 6. A telechelic polyamide,according to claim 4, wherein said

unit is derived from polymerizing diamine monomers including piperazine.7. (canceled)
 8. A telechelic polyamide, according to claim 1, whereinsaid polyamide had two carboxyl end groups and was reacted with apolyether molecule having one terminal amine and one terminal hydroxylgroup or two terminal hydroxyl groups to provide endblocks for saidtelechelic polyamide, said polyamide after adding said endblocks havingat least 80 mole % terminal primary or secondary hydroxyl end groups. 9.A telechelic polyamide, according to claim 1, having functional endgroups, wherein at least 80 mole % the functional end groups are primaryor secondary hydroxyl groups.
 10. (canceled)
 11. A telechelic polyamide,according to claim 1, wherein the telechelic polyamide has a weightaverage molecular weight from about 200 to 10,000 g/mole.
 12. Atelechelic polyamide, according to claim 1, wherein the telechelicpolyamide has a weight average molecular weight from about 200 to 5,000g/mole.
 13. A telechelic polyamide, according to claim 11, wherein saidtelechelic polyamide without solvents has viscosity of less than 100,000cps at 70° C. as measured by a Brookfield circular disc viscometer withthe circular disc spinning at 5 rpm.
 14. A telechelic polyamide,according to claim 11, wherein said telechelic polyamide withoutsolvents has viscosity of less than 100,000 cps at 60° C. as measured bya Brookfield circular disc viscometer with the circular disc spinning at5 rpm.
 15. A telechelic polyamide, according to claim 1, wherein saidtelechelic polyamide further comprises at least one oligomer segmentselected from the group of a polyester segment, a polyether segment, anda polycarbonate segment.
 16. A telechelic polyamide, according to claim1, wherein said polyamide had two carboxyl end groups and was reactedwith an amino alcohol having 3 to 16 carbon atoms and having onesecondary amine group and one hydroxyl group to provide hydroxylterminal groups for said telechelic polyamide, said polyamide afteradding said terminal hydroxyl groups having at least 80 mole % terminalprimary or secondary hydroxyl end groups.
 17. A telechelic polyamidecomprising: a) two functional end groups selected from hydroxyl orcarboxyl; b) a polyamide segment comprising at least two amide linkagescharacterized as being derived from reacting an amine with a carboxylgroup, and said polyamide segment comprising repeat units derived frompolymerizing two or more of monomers selected from lactams,aminocarboxylic acids, dicarboxylic acids, and diamines; wherein atleast 25% of the amide linkages are derived from reacting a secondaryamine group with a carboxyl group, and said telechelic polyamide ischaracterized as a liquid with a viscosity of less than 100,000 cps at70° C. as measured by a Brookfield circular disc viscometer with thecircular disc spinning at 5 rpm wherein at least 60 wt. % of saidtelechelic polyamide segment comprises repeat units of the structure

wherein R_(a) is the alkylene portion of the dicarboxylic acid and is acyclic, linear, or branched alkylene of 2 to 36 carbon atoms, optionallyincluding up to 1 heteroatom per 3 or 10 carbon atoms of the diacid, andwherein R_(b) is a linear or branched alkylene of 2 to 60 carbon atomsand optionally being or including cyclic, heterocyclic, alkylene groupand optionally containing up to 1 or 3 heteroatoms per 10 carbon atoms;and R_(c) and R_(d) connect together to form a single linear or branchedalkylene group of 1 to 8 carbon atoms.
 18. A telechelic polyamide,according to claim 17, wherein said telechelic polyamide ischaracterized by a weight average molecular weight from about 200 to10,000 g/mole and comprises a diversity of amide forming repeating unitsdisrupting hydrogen bonding between amide components.
 19. A telechelicpolyamide, according to claim 17, wherein said two functional end groupswere primary or secondary amine groups and said telechelic polyamide wasreacted with a lactone of 2 or 4 to 10 carbon atoms and/or hydroxylcarboxylic acid of 3 to 30 carbon atoms to create one or more hydroxylfunctional end group derived from said lactone or said hydroxylcarboxylic acid.
 20. A telechelic polyamide, according to claim 19,wherein two functional hydroxyl end groups per polyamide are generatedby said reaction of said telechelic polyamide with said lactone and/orsaid hydroxyl carboxylic acid.
 21. A telechelic polyamide, according toclaim 17 wherein said telechelic polyamide is characterized by havingtwo terminal hydroxyl groups derived from reacting a telechelicpolyamide having two terminal carboxyl end groups with an amino alcoholhaving 3 to 16 carbon atoms and said amino alcohol having one secondaryamine group and one hydroxyl group to provide hydroxyl terminal groupsfor said telechelic polyamide.
 22. A telechelic polyamide comprising: a)repeat units derived from polymerizing monomers connected by linkagesbetween the repeat units and functional end groups selected fromcarboxyl or primary or secondary amine, wherein at least 70 mole percentof telechelic polyamide have exactly two functional end groups of thesame functional type selected from the group consisting of primary orsecondary hydroxyl end groups; and b) a polyamide segment comprising atleast two amide linkages characterized as being derived from reacting anamine with a carboxyl group, and said polyamide segment comprisingrepeat units derived from polymerizing two or more of monomers selectedfrom lactams, aminocarboxylic acids, dicarboxylic acids, and diamines;and wherein at least 90% of the total number of the heteroatomcontaining linkages connecting hydrocarbon type linkages arecharacterized as being amide.